CN111774574A - Preparation and application of Al-Bi-containing compound porous block hydrogen production material - Google Patents
Preparation and application of Al-Bi-containing compound porous block hydrogen production material Download PDFInfo
- Publication number
- CN111774574A CN111774574A CN202010695467.8A CN202010695467A CN111774574A CN 111774574 A CN111774574 A CN 111774574A CN 202010695467 A CN202010695467 A CN 202010695467A CN 111774574 A CN111774574 A CN 111774574A
- Authority
- CN
- China
- Prior art keywords
- hydrogen production
- containing compound
- powder
- ball milling
- porous block
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1134—Inorganic fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an Al-Bi-containing compound porous block hydrogen production material, which is prepared by ball-milling and mixing raw material Al powder and a Bi-containing compound and then sintering through discharge plasma; the Bi-containing compound of the composite hydrogen production material has to meet the requirements that the Bi-containing compound does not react with Al powder in the ball milling process and can react to generate gas in the discharge plasma sintering process, so that the composite hydrogen production material forms a porous shape. The Bi compound is Bi2O2CO3，Bi2O2CO3Carbon dioxide gas is generated during the spark plasma sintering process. The preparation method comprises the following steps: 1) ball milling process; 2) and (3) a spark plasma sintering process. The hydrogen production amount is 1070 < - > and 1200 mL & g < - > by reacting with water as the application of the hydrolysis hydrogen production material‑1The hydrogen production rate can reach 93-95%, and the apparent activation energy of the material reacting with water is 29-30 KJ·mol‑1. The invention has the following advantages: 1. gas is generated in the spark plasma sintering process, and the contact area of the material and water is increased by the holes formed in the composite material; 2. formation of Bi and Bi2O3And the hydrogen production performance of the composite material is improved.
Description
Technical Field
The invention belongs to the technical field of energy, and particularly relates to preparation and application of an Al-Bi-containing compound porous block hydrogen production material.
Background
Among various energy sources, hydrogen energy has received extensive attention and research due to its advantages of environmental friendliness, wide sources and the like, and the preparation and storage of hydrogen energy have been the key points of hydrogen energy research. The method for preparing hydrogen by using the aluminum water reaction is an efficient and clean hydrogen preparation method, and the aluminum-based hydrogen production material has the advantages of high energy density, low raw material cost, no pollution of products and the like, so that the method has long-term application prospect.
The main preparation method of the current aluminum-based hydrogen production material is to adopt a high-energy ball milling method and realize the compounding of a metal bismuth simple substance by initiating the in-situ reaction of a bismuth-containing compound and aluminum powder. For example, the inventors' topic group related work (ZL201510359876. X, an Al-BiBr)3Aluminium base composite hydrogen producing material and its prepn process]) The technique is carried out by BiBr3In-situ reaction with Al powder in the high-energy ball milling process to obtain BiBr3Reducing the Bi into Bi, and improving the hydrogen production performance of the aluminum matrix composite by utilizing the Bi generated in situ, when BiBr31189 mL/g can be obtained when the doping amount reaches 10 percent-1Hydrogen production amount and hydrogen production rate of 98.3%. However, the technical problem of the technology is that the prepared aluminum-based composite hydrogen production material is a powder material, the reaction process of the powder material and water is not controlled and the powder material does not react with waterConvenient carrying and feeding and the like.
Similar work is also done by prior art Chen et al (Chen C, Lan B, Liu K, et al, Anovel aluminum/bismuth subcarbonate/salt composition for hydrogen generation from tap water [ J ]]Journal of Alloys and Compounds, 2019, 808: 151733.) by Bi using a high energy ball milling method2O2CO3In-situ reaction with Al powder in the high-energy ball milling process to react Bi2O2CO3Decomposed and reduced to Bi and Bi2O3And CO2Using in situ generated Bi and Bi2O3The hydrogen production performance of the aluminum-based composite material is improved, the technology also has the problem that the aluminum-based composite material is powder, and the doping amount needs to be 15 percent to realize 820mL g-1Hydrogen production amount and hydrogen production rate of 70.9%.
To solve the problem of the powder material, the present inventors have worked on a group of subjects, Lepeng et al (ZL201710494703.8, preparation of an aluminum-based composite hydrogen production material by spark plasma sintering, and applications thereof [ P]) Al powder, Bi powder and various carbon materials are sintered by using SPS plasma sintering technology to prepare the aluminum-based block hydrogen production material. Realizes that the reaction of the Al-Bi-G bulk material with water can reach 1169.1 mL-G under the condition of 333.15K-1The hydrogen production rate and the hydrogen production rate of 90.1 percent are greatly improved compared with the powder material which is not sintered, but the technical problems that the graphene raw material is expensive and the structure of the sintered block is compact, so that the hydrogen production rate cannot meet the application requirement still exist.
Disclosure of Invention
The invention aims to provide preparation and application of an Al-Bi-containing compound porous block hydrogen production material.
In order to form the pore morphology in the material by the gas generated in the sintering process of the material and realize the in-situ doping of Bi and Bi2O3Effectively obtain the effect of catalyzing hydrogen production, and select Bi which can generate gas due to decomposition in the sintering process2O2CO3As raw material, by decompositionCO of2The formation of abundant hole microscopic morphologies on the surface of the Al is realized;
as known in the art, Bi2O2CO3Decomposition occurs during the high-energy ball milling process, and the technical effects cannot be realized if corresponding technical treatment is not carried out, so that Al and Bi are realized2O2CO3On the basis of uniform mixing, avoiding Bi2O2CO3Decomposition occurs during the ball milling process, and proper ball milling conditions need to be adjusted.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation of the Al-Bi-containing compound porous block hydrogen production material comprises the steps of ball-milling and mixing raw material Al powder and a Bi-containing compound, and then sintering the mixture by discharge plasma to obtain the Bi-containing compound, wherein the Bi-containing compound has the following two characteristics that firstly the Bi-containing compound cannot be decomposed and does not react with the Al powder in the ball-milling process, and secondly the Bi-containing compound can be decomposed and reacts with the Al powder in the discharge plasma sintering process to generate gas, so that the composite hydrogen production material has a porous appearance; the Bi compound is Bi2O2CO3，Bi2O2CO3Carbon dioxide gas is generated during the spark plasma sintering process.
The preparation method of the Al-Bi-containing compound porous block hydrogen production material comprises the following steps:
step 1) ball milling process, under the protection of argon atmosphere, according to the mass ratio of Al powder and Bi compound, Bi2O2CO3The doping amount of the Al powder is 10-15%, Al powder and Bi compound are weighed, the ball-to-material ratio is 20:1, and the ball milling rotating speed is 20-80 r.min-1Ball milling is carried out for 20-60min to obtain Al-Bi which is uniformly mixed2O2CO3A powder material;
step 2) discharge plasma sintering process, Al-Bi obtained in step 12O2CO3The heating rate of the powder material is 100 ℃ min-1Sintering at 500 deg.C for 10 min under 20 MPa to obtain Al-Bi2O2CO3A porous block hydrogen production material.
Al-Bi2O2CO3The porous block hydrogen production material is applied as a hydrogen production material, and the hydrogen production amount of the material is 1070-1200 mL-g after the material reacts with water-1The hydrogen production rate can reach 93-95%, and the apparent activation energy of hydrolysis reaction is 29-30 KJ.mol-1。
Adding Bi2O2CO3Al-Bi prepared by ball milling with Al2O2CO3Powder material and Al-Bi prepared by ball milling and spark plasma sintering2O2CO3XRD analysis is respectively carried out on the porous block hydrogen production material, and the result shows that only Al peak and Bi exist in the ball-milled aluminum-bismuth mixed powder material2O2CO3Peak of (b) indicates Bi in the ball milling process2O2CO3No decomposition reaction occurred. And Al-Bi prepared by ball milling and spark plasma sintering2O2CO3Bi in porous block material2O2CO3The peak of (A) is completely disappeared, and Bi appear2O3Peak of (2), evidence of Bi in the sintering process2O2CO3Thermal decomposition to produce Bi and Bi2O3Bi and Bi2O3Can better catalyze Al hydrolysis to produce hydrogen.
And Al-Bi prepared by ball milling2O2CO3Powder material and Al-Bi prepared by ball milling and spark plasma sintering2O2CO3SEM appearance analysis is respectively carried out on the porous block hydrogen production material, and the result shows that the surface of the Al particles after ball milling is smooth and has no holes, and Bi2O2CO3Uniformly distributed on the surface of the Al particles; but a large number of holes appear on the surface of the Al after sintering treatment, and the holes increase the contact area of the Al and water and are beneficial to improving the reaction speed of the Al and the water.
Al-Bi prepared by ball milling and spark plasma sintering2O2CO3The hydrogen production performance of the porous block hydrogen production material is tested at different reaction temperatures, and the apparent activation energy is calculated to be 29.7 KJ.mol according to the maximum reaction rate-1. This value is much lower than the apparent activation energy value (42.5-68.4 KJ. mol.) of aluminum reacting with water in strong alkaline solution-1) It shows that the Al-Bi of the present invention2O2CO3The porous block material has excellent reactivity.
And Al-Bi prepared by spark plasma sintering under different pressure intensities2O2CO3SEM morphology analysis is respectively carried out on the porous block hydrogen production materials, and the result shows that Al-Bi obtained under 10 MPa2O2CO3The bulk hydrogen production material had fewer pores, indicating that the pressure was not sufficient to force CO2Enough holes are generated in the material to enhance the hydrogen production performance of the material. Under 30 MPa, the hydrogen production material of the block body has dense holes, but the holes are not uniformly distributed; the hydrogen production material with dense holes and uniformly distributed blocks can be obtained only under 20 MPa, which shows that 20 MPa is the optimal sintering pressure.
Al-Bi according to the invention2O2CO3The hydrogen production performance of the porous block hydrogen production material is tested by adopting a drainage gas collection method, and 0.5 g of prepared Al-Bi is weighed2O2CO3A porous block hydrogen production material; 30 mL of water was added at 333.15K, and the produced gas was collected and its hydrogen-producing performance was measured.
The experimental detection result of the hydrogen production performance of the block hydrogen production material is as follows: under the conditions of neutral solution and 333.15K, the unit hydrogen yield is 1074--1The maximum hydrogen production rate is 385-423 mL-g-1·min-1And a conversion of 93-95%.
The invention has the following advantages:
1. the preparation method is rapid, energy-saving and environment-friendly;
2. bi in spark plasma sintering2O2CO3Is thermally decomposed to generate Bi and Bi2O3And CO2。CO2Holes are generated on the block hydrogen production material, and the holes increase the contact area of the material and water;
3. generated Bi and Bi2O3Can improve the hydrogen production performance of Al and water reaction. Sintering with other plasmasCompared with the prepared aluminum-based block hydrogen production material (ZL201710494703.8, preparation and application of aluminum-based composite hydrogen production material sintered by discharge plasma [ P]) The block material provided by the invention reduces the cost of raw materials and improves the hydrogen production performance.
Therefore, the invention has simple manufacturing process, low cost of raw materials, no pollution of products and high hydrogen production efficiency, and can be used as a hydrogen source of a fuel cell.
Drawings
FIG. 1 shows Bi2O2CO3Material, aluminum-bismuth powder material prepared by ball milling and Al-Bi prepared by ball milling and spark plasma sintering2O2CO3XRD pattern of porous bulk material;
FIG. 2 shows 90% Al-10% Bi2O2CO3SEM picture of powder material;
FIG. 3 shows Al-Bi obtained by spark plasma sintering at 20 MPa2O2CO3SEM picture of the porous block hydrogen production material;
FIG. 4 shows 90% Al-10% Bi2O2CO3Ln of porous block hydrogen production materialkTo 1000TDrawing;
FIG. 5 shows Bi with different doping contents2O2CO3Al-Bi of2O2CO3A hydrogen production curve of the porous block hydrogen production material subjected to hydrolysis reaction at 333.15K, wherein a is hydrogen production amount, b is hydrogen production rate, and c is a hydrogen production rate curve;
FIG. 6 shows 90% Al-10% Bi obtained by spark plasma sintering at 10 MPa2O2CO3SEM picture of the porous block hydrogen production material;
FIG. 7 shows 90% Al-10% Bi obtained by spark plasma sintering at 30 MPa2O2CO3SEM image of porous block hydrogen production material.
Detailed Description
The invention is further described in detail by the embodiments and the accompanying drawings, but the invention is not limited thereto.
Example 1
Al-Bi2O2CO3The preparation of the porous block hydrogen production material and the hydrogen production performance test comprise the following steps:
step 1) ball milling process, under the protection of argon atmosphere, according to Al powder and Bi2O2CO3Weighing Al powder and Bi according to the mass ratio of 17:32O2CO3The ball-material ratio is 20:1, the ball milling speed is 50 r.min-1And ball milling is carried out for 30 min to obtain uniformly mixed Al-Bi2O2CO3A powder material;
step 2) discharge plasma sintering process, Al-Bi obtained in step 12O2CO3The heating rate of the powder material is 100 ℃ min-1Sintering at 500 deg.C for 10 min under 20 MPa to obtain Al-Bi2O2CO3A porous bulk material. The obtained Al-Bi2O2CO3The porous block hydrogen production material is named as 90% Al-10% Bi2O2CO3。
Firstly, in order to prove the respective functions of the ball milling process and the discharge plasma sintering process in the technical scheme, XRD analysis is carried out on the powder material obtained in the step 1 and the block composite hydrogen production material obtained in the step 2, and the result is shown in figure 1.
FIG. 1 shows Al-Bi obtained after ball milling2O2CO3Only Al and Bi exist in XRD curve of powder material2O2CO3Peak of (3), demonstrating that no Bi occurs during ball milling2O2CO3Self-decomposition or oxidation-reduction reaction with Al, i.e. the ball-milling process only functions to make Al and Bi2O2CO3The function of uniform mixing;
and Al-Bi obtained after spark plasma sintering2O2CO3In XRD curve of porous bulk material, Al peak still exists, but Bi2O2CO3The peak of (A) disappears completely, and Bi appear2O3New peak of (2), demonstration of firing in discharge plasmaIn the junction process, Bi2O2CO3Self-decomposition occurs and oxidation-reduction reaction occurs with Al.
② in order to prove the influence of the generated gas on the microstructure of the block hydrogen production material in the spark plasma sintering process, the Al-Bi obtained in the step 1 is subjected to2O2CO3Powder material and Al-Bi obtained in step 22O2CO3SEM analysis of the porous bulk material is shown in figures 2 and 3.
Al-Bi2O2CO3The microstructure of the powder material is shown in FIG. 2. from FIG. 2, it can be seen that the surface of the aluminum particles is smooth and has no pores, while Bi is present2O2CO3Uniformly distributed on the surface of the aluminum particles;
Al-Bi2O2CO3the microstructure of the porous block hydrogen production material is shown in fig. 3, and it can be known from fig. 3 that a large number of pores appear on the surface of the sintered aluminum particles.
According to SEM analysis and XRD experiment results, a large number of holes are formed on the surface of aluminum particles by carbon dioxide gas generated by decomposition in the discharge plasma sintering process, so that the contact area of the material and water is increased, and the hydrogen production performance of the material is improved.
③ to prove the influence of the spark plasma sintering process on the hydrogen production performance, the Al-Bi obtained in step 12O2CO3Powder material and Al-Bi obtained in step 22O2CO3The porous block material is subjected to hydrogen production performance test, and the test results are shown in the following table 1.
TABLE 1 Al-Bi2O2CO3Powder material and Al-Bi2O2CO3Hydrogen production performance of porous block hydrogen production material
As shown in Table 1, the powder material has almost no hydrogen production performance, while the porous block hydrogen production material has excellent hydrogen production performance, which shows that the discharge plasma sintering is favorable for improving Al-Bi2O2CO3The hydrogen production performance of the catalyst.
④ to prove the Al-Bi of the invention2O2CO3The reaction kinetics performance of the porous block material is tested under the temperature conditions of 303.15K, 313.15K, 323.15K, 333.15K and 343.15K, and the hydrogen production performance and the activation energy are calculated, and the results are shown in Table 2.
TABLE 2 at various temperatures, 90% Al-10% Bi2O2CO3Hydrogen production performance of porous block hydrogen production material
Ln is plotted according to the Allen-wutz formula and Table 2k-1000/TCurves (as shown in fig. 4); the apparent activation energy of the reaction of the porous block hydrogen production material and water is calculated to be 29.7 KJ.mol-1. This value is much lower than the apparent activation energy (42.5-68.4 KJ. mol) of aluminum reacting with water in strong alkaline solution-1) The surface of the aluminum-based porous block material has excellent reaction activity.
⑤ to demonstrate the difference Bi2O2CO3Doping amount to Al-Bi2O2CO3The influence of the hydrogen production performance of the porous block material prepares Bi2O2CO3Al-Bi with doping amounts of 5%, 15%, 20% and 25%, respectively2O2CO3A porous bulk material. (see FIG. 5 for results)
Comparative example 1
Al-Bi2O2CO3The preparation method of the porous block hydrogen production material and the hydrogen production performance test are the same as those in the embodiment 1, wherein the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: in the step 1, 2.85 g of Al powder and 0.15 g of Bi are weighed2O2CO3The obtained aluminum-based porous block hydrogen production material is named as 95 percent Al-5 percent Bi2O2CO3。
Example 2
Al-Bi2O2CO3Porous block hydrogen production materialThe preparation method of the material and the hydrogen production performance test are the same as those in the embodiment 1, wherein the steps which are not particularly described in the concrete steps are the same as those in the embodiment 1; the difference lies in that: step 1, weighing 2.55 g of Al powder and 0.45 gBi2O2CO3The obtained aluminum-based porous block material is named as 85% Al-15% Bi2O2CO3。
Comparative example 2
Al-Bi2O2CO3The preparation method of the porous block material and the hydrogen production performance test are the same as those in the embodiment 1, wherein the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: step 1, weighing 2.4 g of Al powder and 0.6 gBi2O2CO3The obtained aluminum-based composite hydrogen production material is named as 80 percent of Al-20 percent of Bi2O2CO3。
Comparative example 3
Al-Bi2O2CO3The preparation method of the porous block material and the hydrogen production performance test are the same as those in the embodiment 1, wherein the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: step 1, weighing 2.25 g of Al powder and 0.75 gBi2O2CO3The obtained aluminum-based composite hydrogen production material is named as 75 percent Al-25 percent Bi2O2CO3。
TABLE 4 at 333.15K, with different Bi2O2CO3Content of Al-X wt% Bi2O2CO3Hydrogen generation performance of porous block material
The experimental result shows that the increase of Bi2O2CO3The content can effectively increase the reaction rate and improve the hydrogen production performance of the material, wherein the sample contains 90 percent of Al and 10 percent of Bi2O2CO3The hydrogen production performance is optimal, and the hydrogen production amount reaches 1161.8mL g-1The corresponding hydrogen production rate and hydrogen production conversion rate are 385mL g-1min-1And 94.9%. The hydrogen production conversion rate of the sample is 5 to 20 percent when the catalyst content isAbove 80%. Compared with the Al-Bi-G discharging plasma sintering block material of Lepeng et Al (patent number: ZL 201710494703.8), the catalyst prepared by the method has better catalytic effect, and the material prepared by the method has higher application value.
⑥ to prove the accelerating effect of the sintering process on the hydrogen production performance of the material, Chen et al found that the sintering process was at 500 r.min-185-15% Bi prepared by ball milling for 6h2O2CO3The hydrogen production performance of the composite material is compared, and the result is shown in table 3.
TABLE 385% Al-15% Bi2O2CO3Comparison of Hydrogen production Performance between Block and powder Material
The comparison shows that Bi caused by discharge plasma sintering is more than Bi caused by ball milling2O2CO3CO produced by decomposition2Bi and Bi2O3Has better catalytic activity.
⑦ to demonstrate different sintering pressures for Al-Bi2O2CO3The sintering pressures of 90 percent of Al and 10 percent of Bi with 10 MPa and 30 MPa respectively are prepared under the influence of the hydrogen production performance of the porous block hydrogen production material2O2CO3A porous bulk material.
Comparative example 4
Al-Bi2O2CO3The preparation method of the porous block material and the hydrogen production performance test are the same as those in the embodiment 1, wherein the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; the difference lies in that: the sintering pressure in the step 2 is 10 MPa, and the obtained aluminum-based composite hydrogen production material is named as 90% Al-10% Bi2O2CO3-10 MPa. SEM testing of this material was also performed, and the results are shown in fig. 6.
Comparative example 5
Al-Bi2O2CO3The preparation method of the porous block hydrogen production material and the hydrogen production performance test are the same as those in the embodiment 1, wherein the steps which are not particularly described in the specific steps are the same as those in the embodiment 1; is not limited toThe method is characterized in that: the sintering pressure in the step 2 is 30 MPa, and the obtained aluminum-based composite hydrogen production material is named as 90% Al-10% Bi2O2CO3-30 MPa. SEM testing of this material was also performed, and the results are shown in fig. 7.
TABLE 5 90% Al-10% Bi obtained at 333.15K and different sintering pressures2O2CO3Hydrogen production performance of porous block hydrogen production material
As can be observed from the SEM topography of the porous block materials prepared under different pressures in the graphs of FIGS. 3, 6 and 7, the block material has fewer pores under the sintering pressure of 10 MPa, and the sintering pressure is not enough to force CO2Enough holes are generated in the material to enhance the hydrogen production performance of the material; the bulk material under the sintering pressure of 30 MPa has small and dense holes, but the hole distribution is not uniform; the sizes of the holes in the block material are consistent and uniformly distributed under the sintering pressure of 20 MPa.
Experimental results show that the hydrogen production rate of the material can be effectively increased and the hydrogen production rate can be increased by increasing the sintering pressure, and the hydrogen production rate of the material is improved by finding that the smaller the pore size of the material and the more uniform the distribution of the pores are according to the shape analysis of SEM under different sintering pressures, wherein the sintering pressure is 90% Al-10% Bi of 20 MPa2O2CO3The sample hydrogen production performance is optimal.
Claims (7)
- An Al-Bi-containing compound porous block hydrogen production material, which is characterized in that: ball-milling and mixing Al powder and a Bi-containing compound as raw materials, and sintering by discharge plasma to obtain the material;the Bi-containing compound has the following two characteristics that firstly, the Bi-containing compound cannot be decomposed and does not react with Al powder in the ball milling process, and secondly, the Bi-containing compound can be decomposed and reacts with Al powder in the discharge plasma sintering process to generate gas, so that the composite hydrogen production material forms a porous shape.
- 2.The Al-Bi containing compound porous block hydrogen production material according to claim 1, characterized in that: the Bi compound is Bi2O2CO3，Bi2O2CO3Carbon dioxide gas is generated during the spark plasma sintering process.
- 3. The method for producing an Al-Bi containing compound porous block hydrogen production material according to claim 1, characterized by comprising the steps of:step 1), in a ball milling process, weighing Al powder and a Bi compound according to a certain mass ratio of the Al powder and the Bi compound under the protection of argon gas, and performing ball milling under certain conditions to obtain an aluminum-bismuth mixed powder material which is uniformly mixed;step 2) a spark plasma sintering process, wherein the aluminum bismuth mixed powder material obtained in the step 1 is subjected to spark plasma sintering under certain conditions to obtain Al-Bi2O2CO3A porous block hydrogen production material.
- 4. The production method according to claim 3, characterized in that: the Bi compound in the step 1 is Bi2O2CO3The mass ratio of the Al powder and the Bi compound in the step 1 satisfies Bi2O2CO3The doping amount of (A) is 10-15%.
- 5. The production method according to claim 3, characterized in that: the ball milling condition in the step 1) is that the ball-material ratio is 20:1, and the ball milling rotating speed is 20-80 r.min-1And the ball milling time is 20-60 min.
- 6. The production method according to claim 3, characterized in that: the sintering condition of the step 2) is that the heating rate is 100 ℃ min-1The sintering temperature is 500 ℃, the heat preservation time is 10 min and the sintering pressure is 20 MPa.
- 7. The use of the Al-Bi-containing compound porous bulk hydrogen production material according to claim 1 as a hydrolysis hydrogen production material,the method is characterized in that: spark plasma sintered Al-Bi2O2CO3The hydrogen yield of the porous block hydrogen production material after reaction with water is 1070 < - > 1070 mL & g-1The hydrogen production rate can reach 93-95%, and the apparent activation energy of hydrolysis reaction is 29-30 KJ.mol-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010695467.8A CN111774574B (en) | 2020-07-20 | 2020-07-20 | Preparation and application of Al-Bi-containing compound porous block hydrogen production material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010695467.8A CN111774574B (en) | 2020-07-20 | 2020-07-20 | Preparation and application of Al-Bi-containing compound porous block hydrogen production material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111774574A true CN111774574A (en) | 2020-10-16 |
| CN111774574B CN111774574B (en) | 2022-08-30 |
Family
ID=72763540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010695467.8A Active CN111774574B (en) | 2020-07-20 | 2020-07-20 | Preparation and application of Al-Bi-containing compound porous block hydrogen production material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111774574B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB924715A (en) * | 1960-05-24 | 1963-05-01 | Lor Corp | Foaming granulated metal |
| JP2005162552A (en) * | 2003-12-04 | 2005-06-23 | National Institute For Materials Science | Composite material for hydrogen generation and its manufacturing method |
| CN101284647A (en) * | 2008-02-29 | 2008-10-15 | 邓振炎 | Hydrogen preparing process by reacting surface-modified pure alminuim powder with water |
| CN106132598A (en) * | 2014-05-16 | 2016-11-16 | 三菱综合材料株式会社 | Porous aluminum sintered body and the manufacture method of porous aluminum sintered body |
| CN107338372A (en) * | 2017-06-26 | 2017-11-10 | 桂林电子科技大学 | A kind of preparation and its application of the aluminum-based composite hydrogen manufacturing material of discharge plasma sintering |
| CN107352507A (en) * | 2017-07-04 | 2017-11-17 | 桂林电子科技大学 | A kind of Al InCl3The preparation method and applications of (Ni Bi B) aluminum-based composite hydrogen manufacturing material |
| CN107848797A (en) * | 2015-07-15 | 2018-03-27 | Hrl实验室有限责任公司 | Spherical nanoparticle hydride and preparation method thereof |
| CN109133000A (en) * | 2018-08-23 | 2019-01-04 | 杭州氢源素生物科技有限公司 | A kind of micro-nano composite hydrolysis hydrogen manufacturing material of aluminium base |
| CN109252187A (en) * | 2018-09-10 | 2019-01-22 | 武汉理工大学 | A kind of high-entropy alloy elctro-catalyst, preparation method and the application of water decomposition hydrogen manufacturing |
-
2020
- 2020-07-20 CN CN202010695467.8A patent/CN111774574B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB924715A (en) * | 1960-05-24 | 1963-05-01 | Lor Corp | Foaming granulated metal |
| JP2005162552A (en) * | 2003-12-04 | 2005-06-23 | National Institute For Materials Science | Composite material for hydrogen generation and its manufacturing method |
| CN101284647A (en) * | 2008-02-29 | 2008-10-15 | 邓振炎 | Hydrogen preparing process by reacting surface-modified pure alminuim powder with water |
| CN106132598A (en) * | 2014-05-16 | 2016-11-16 | 三菱综合材料株式会社 | Porous aluminum sintered body and the manufacture method of porous aluminum sintered body |
| CN107848797A (en) * | 2015-07-15 | 2018-03-27 | Hrl实验室有限责任公司 | Spherical nanoparticle hydride and preparation method thereof |
| CN107338372A (en) * | 2017-06-26 | 2017-11-10 | 桂林电子科技大学 | A kind of preparation and its application of the aluminum-based composite hydrogen manufacturing material of discharge plasma sintering |
| CN107352507A (en) * | 2017-07-04 | 2017-11-17 | 桂林电子科技大学 | A kind of Al InCl3The preparation method and applications of (Ni Bi B) aluminum-based composite hydrogen manufacturing material |
| CN109133000A (en) * | 2018-08-23 | 2019-01-04 | 杭州氢源素生物科技有限公司 | A kind of micro-nano composite hydrolysis hydrogen manufacturing material of aluminium base |
| CN109252187A (en) * | 2018-09-10 | 2019-01-22 | 武汉理工大学 | A kind of high-entropy alloy elctro-catalyst, preparation method and the application of water decomposition hydrogen manufacturing |
Non-Patent Citations (5)
| Title |
|---|
| CHEN CHEN等: "A novel aluminum/bismuth subcarbonate/salt composite for hydrogen generation from tap water", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| CHONG ZHAO等: "A novel AleBiOCl composite for hydrogen generation from water", 《SCIENCEDIRECT》 * |
| MEI-QIANG FAN等: "Hydrolysis of ball milling Al–Bi–hydride and Al–Bi–salt mixture for hydrogen generation", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 赵冲等: "铝基材料水解制氢技术", 《化学进展》 * |
| 陈晨等: "Bi在铝基复合材料水解制氢中的作用", 《特种铸造及有色合金》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111774574B (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Issues and opportunities facing hydrolytic hydrogen production materials | |
| Zou et al. | Preparation and characterization of hydro-reactive Mg–Al mechanical alloy materials for hydrogen production in seawater | |
| CN102030313B (en) | Organic matter and ammonia borane compounded hydrogen storage material and preparation method thereof | |
| Dong et al. | Enhanced hydrogen sorption properties of MgH2 when doped with mechanically alloyed amorphous Zr0· 67Ni0. 33 particles | |
| CN115140743B (en) | Two-dimensional metal boride and hydrothermal auxiliary alkali liquor etching preparation method and application | |
| CN106744680B (en) | A kind of Al-LiH- metal oxide hydrogen manufacturing material and preparation method thereof | |
| Hu et al. | Improvement in hydrogen storage performance of Mg by mechanical grinding with molten salt etching Ti3C2Clx | |
| Xu et al. | Magnesium-Based Hydrogen Storage Alloys: Advances, Strategies, and Future Outlook for Clean Energy Applications | |
| CN109052403B (en) | Two-dimensional titanium carbide-doped lithium aluminum hydride hydrogen storage material and preparation method thereof | |
| Naseem et al. | A reusable dual functional Mo 2 C catalyst for rapid hydrogen evolution by Mg hydrolysis | |
| CN111573621B (en) | Method for preparing hydrogen by hydrolysis | |
| CN101920973B (en) | Method for preparing porous aluminum diboride | |
| ZHANG et al. | Catalytic effect of two-dimensional Mo2TiC2 MXene for tailoring hydrogen storage performance of MgH2 | |
| Song et al. | Comparison of the hydrogen release properties of Zn (BH 4) 2-added MgH 2 alloy and Zn (BH 4) 2 and Ni-added MgH 2 alloy | |
| CN111774574B (en) | Preparation and application of Al-Bi-containing compound porous block hydrogen production material | |
| CN102765723B (en) | Method for synthesizing KSi hydrogen storage alloy | |
| CN107585738B (en) | Mg-Mg2Si composite hydrolysis hydrogen production material, preparation method thereof and method for hydrolysis hydrogen production | |
| Zhang et al. | Effect of LaFeO3 on hydrogenation/dehydrogenation properties of MgH2 | |
| WO2024000963A1 (en) | Aluminum/carbon composite for hydrogen production by means of reaction with alkaline water, and preparation method therefor and use thereof | |
| CN115957734A (en) | Catalyst and preparation method thereof, and hydrogen storage material containing catalyst and preparation method thereof | |
| CN103288047B (en) | Hydroboron/graphite fluoride nano-composite hydrogen storage material and preparation method thereof | |
| Wang et al. | Hydrogen generation from the reaction of Al-7.5 wt% Li-25 wt% Co/NaBH4 powder and pure water | |
| CN113562694B (en) | Hydrolysis hydrogen production method based on magnesium-based composite material | |
| CN115367701B (en) | MgH (MgH) 2 -AlH 3 -TiF 3 Composite hydrogen storage material and preparation method thereof | |
| Wu et al. | Novel porous Al-based composites for improved Al–water reaction performances by spark plasma sintering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |